Epoxy resin copolymers



3,679,367 EPGXY REiN CUPOLYMERS Paul Fram, Lincoln Township, and Robert R. Charltonneau, Woodhury Township, Washington County, Minn, assignors to Minnesota Mining and Manufacturing Company, St. Paul, Minn, a corporation of Delaware No Drawing. Filed Mar. 3t), 1959, Ser. No. 802,631

8 Claims. (Cl. 260--47) This invention relates to copolymeric compositions and more particularly to copolymers of epoxy resins with certain polyfunctional alkylenimine derivatives.

Monomers and low polymers containing functional epoxy groups, which are collectively termed epoxy resins hereinafter for convenience and brevity, are well known.

These substances are readily prepared, for example, by the interaction of epichlorohydrin with a polyhydric phenol. They are commonly cured or copolymerized with such compounds as polyfunctional amines, organic acids, acid anhydrides, and the like. Certain of the epoxy resins cure to form solid polymers which have the excellent strength and heat resistance properties required in various high performance applications, e.g. in heated plastic dies, radomes and in certain ducting and structural uses. These particular resins, however, have been typically diflicult to process and handle. If, on the other hand, epoxy resins having improved processing and handling characteristics have been used, strength and heat resistance have been sacrificed.

It is an object of the present invention to provide a new and useful class of copolymeric resins. It is another object of the present invention to provide a class of liquid compositions which cure at relatively low temperatures (often at room temperature) without appreciable shrinkage to dense, tough, resinous solids.

It is another object of the present invention to provide a novel and useful class of plastic tooling resins.

It is still another object of the present invention to provide 100 percent solid-forming high temperature resistant resin systems for use in reinforced plastics and other applications requiring ultimate properties equal to or superior to epoxy resin systems and having greatly superior handling and processing characteristics.

Additional objects will be apparent to those skilled in the art from reading the specification which follows.

In accordance with the above and other objects of the invention it has been found that when epoxy resins are copolymerized with the hereinafter-defined polyfunctional alkylenimine derivatives, new resinous compositions are produced which have highly advantageous properties, as set forth hereinafter in detail.

Epoxy resins in general (i.e. those organic compounds containing reactive ethoxyllne groups) are suitable for use in the present invention. Among the epoxy resins useful in the practice of the present invention are complex polymeric reaction products of polyhydric phenols with polyfunctional halohydrins such as epichlorohydrin and glycerol dichlorohydrin. Such resins are disclosed in United States Patent 2,585,115, and in the textbook Epoxy Resins, Their Applications and Technology, by Lee et al., McGraw-Hill Book Company, Inc., New York, N.Y., 1957, particularly in chapter 1 thereof. A table is given at pages 19 and 20 of that book in which are tabulated the basic chemical types, and properties of a number of commercially available epoxy resins. Resins of the type characterized in this table are among the epoxy resins suitable for use in the present invention.

The polyfunctional alkylenimine derivatives employed in preparing the copolymers of the invention are substituted ethylene amides (for convenience, sometimes herein 3,?,37 Patented Feb. 28, 19$?) referred to as bis-amides) of the type represented by the following formula:

wherein R represents a member of the group consisting of divalent aliphatic hydrocarbon radicals having from 6 to 18 carbon atoms, the 1,3-phenylene radical and the 1,4- phenylene radical and R and R each represent hydrogen or a lower alkyl group, i.e. having from 1 to 4 carbon atoms.

The bis-amide-epoxy resin copolymers of the invention, after having been subjected to the curing process, demonstrate a high degree of toughness, resistance to shock and to high temperatures and resistance to water. These characteristics render them useful as potting, molding, casting and laminating resins. Molded objects from these infusible products have hard glossy surfaces but despite this hardness the molded structures are tough and resilient.

Lamination and impregnation of materials such as wood, glass, glass fabric, synthetic fibers such as nylon and Orlon paperboard, etc. are extremely important fields of application for the new compositions. This is particularly true in the impregnation of glass fibers to form reinforced plastic compositions suitable for use for example in automobile bodies, truck and railroad car construction, aircraft construction, industrial piping, etc. In addition, compositions of the invention are valuable in such other varied applications in the field of resin technology as industrial adhesives, protective and decorative coatings, etc.

Depending on the reactivity of the uncured mixtures which cure to form the compositions of the invention, polymerization takes place, generally with only moderate heating if any increase in temperature is required, over varying periods of time. The reactivity of any copolymer system of the invention depends upon such factors as the physical state (solid or liquid) of the constituents, their viscosities, the presence of additives such as solvents, fillers and other resins, as well as upon the catalyst system, if any, which is used. The catalyst system is particularly important in determining the intermediate properties of the copolymers (e.g. pot life, amount and controllahility of exotherm, curing time and temperature, etc.) as well as their ultimate properties (eg. hardness, tensile properties, toughness, impact resistance, high temperature resistance, color, etc.) and therefore their ultimate utility. Thewatalysts which are used in the copolymer systems of this invention are generally speaking the catalysts useful in'epoxy resin polymerization systems, i.e. epoxy-type catalysts. Among the catalysts which can be used with the copolymers of the present invention are amines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, 1,3-pentamethyl diethylene triamine, m-phenylene diamine, the liquid eutectic mixture of m-phenylene diamine and 4-isopropyl-m-phenylene diamine, 4,4'-diamino diphenylsulfone, methylene-bis-o-chloroaniline, menthane diamine, 4,4'-rnethylene dianiline and tridimethyl amino methyl phenol (available commercially under the trade designation DMP-30); catalysts such as coordination compounds of boron trifluoride with amines (e.g. boron trifluoride monomethylamine available commercially under the trade designation BF3-400), with sulfides, etc.; anhydrides such as dodecenyl succinic anhydride, chlorendic anhydride, pyromellitic dianhydride; hydrazides such as adipyl dihydrazide and isophthalyl dihydrazide, and the like.

Depending upon the tion can be conducted solvents or diluents.

particular application, the reacin the presence or absence of In many cases the epoxy resin and/ or the bis-amide will be liquid and the reaction can be effected easily without addition of solvents or diluents. However, in some cases, where either or both reactants are solids, it may be desirable to add diluents to assist in effecting the reaction.

The epoxy resins and the bis-amides are both capable of homopolymerization in the presence of suitable curing agents to solid, resinous compositions. In the case of the epoxy resins these curing agents are generally Well known, cg. polyfunctional amines, organic acids and acid anhydrides, etc. (as previously stated). The homopolymerization of bis-amides is catalyzed by weak or strong acids and bases. Among the acids are the heavy metal chlorides, such as zinc or lead chlorides, the mineral acids, such as hydrochloric, sulfuric or phosphoric acids, sulfonic acids such as p-toluenesulfonic acid, and other acids. Another catalyst which is effective is the boron trifluoride molecular addition product with monoethylamine. Among the bases are sodium methoxide, while amines such as ethylene diamine or monoethanolarnine and hydrazides such as isophthalyl dihydrazide act as curing agents and polyfunctional amines can be copolymerized with the bis-amides. In the presence of a suitable curing .agent, substantially all proportions or" the epoxy resins and the bis-amides may be copolymerized. In mixtures containing a great we ponderance of one or the other constituent, therefore, it is possible to achieve simultaneously polymerization among units of the major constituent itself and between units of the major and minor constituents. The final cured polymer molecules will thus include units of both constituents in the relative amounts in which they were originally added. It should be noted that in order to realize the novel properties of the copolyme'rs of the present invention it is necessary that at least a significant amount of the minor constituent be present. An amount of about 5 percent or more yields a significant change in properties.

I. THE BIS-AMIDES Among the bis-amides useful as comonomers in the present invention are N,N'-bis-1,2-ethylenisosebacamide; N,Nbis-l,2-ethylensebacamide; N,N-'bis-l,Z-ethylensubenamide; N,N-bis-1,2-ethylenazelaamide; N,N'-bis-1,Z-ethylendodecane dicarboxylic acid amide; N,N'-bis-l,Z-ethylentetradecane dicarboxylic acid amide; N,N'-bis-l,2-ethylenhexadecane dicarboxylic acid amide; N,N'-bis-1,Z-ethylenoctadecanedicarboxylic acid amide; N,N-bis-l,Z-butylenisosebacamide; N,'N'-'bis-l,Z-propylensuberamide; N,N-bis-l,2-butylensuberamide; N,N-bis-l,2-propylenazelaamide; N,N'-bis-1,2-butylenazelaamide; N,N'-bis-l,Z-propylentetradecanedicarboxylic acid amide; N,N'-bis-l,2-propylenoctadecanedicarboxylio acid amide; N,N-bis-l,2-propylendodecanedicarboxylic acid amide; N,N-bis-1,2-pentylensebacamide; N,N-bis-1,2-ethylenisophthalamide; N,Nbis-l,Z-ethylenterephthalamide; N,N'-bis-l,Z-butylenisophthalamide; N,N-bis-l,2-propylenisophthalamide; N,N'-bis-1,2-pentylenisophthalamide; N,N-bis-l,Z-propylenterephthalamide.

Mixtures of the bis-amide monomers may be produced by employing mixed 1,2-alkylenimines. Y

The N,N-bis-all ylenamides are prepared in monomeric form by the following process: a 1,2-alkylenimine, desirably containing not more than 6 carbon atoms, such as ethylenimine, 1,2-propylenimine, 1,2-butylenimine, 1,2-pentylenimine, etc., is reacted with an aliphatic hydrocarbon dicarboxylic acid chloride containing 8 to 20 carbon atoms (for example isosebacoyl dichloride, se-

bacoyl dichloride, suberoyl dichloride, azelaoyl dichloride, tetradecanoyl dichloride, dodecanoyl dichloride, hexadecanoyl dichloride, octadecanoyl dichloride), isophthaloyl dichloride or terephthaloyl dichloride, to produce the desired substantially pure N,N'-bis-1,2-alkylenamide monomer, with hydrogen chloride as a oy-product. The 1,2-alkylenimine is employed in a ratio of about 2 moles for each mole of dibasic acid chloride. Advantageously, an excess of 1,2-alkylenimine, such as about 5 percent by weight, over and above this ratio may be employed, although an excess of up to about 25 percent may be employed.

Desirably, the 1,2-alkylenimine is introduced in an aqueous solution which also contains an alkali-metal carbonate, such as sodium, potassium or lithium carbonate, which acts as an acid acceptor to neutralize the hydrogen chloride formed during the reaction of the process. When a higher 1,2-alkylenimine than ethylenimine, i.e., one containing more than 2 carbon atoms, is employed, an alkali-metal bicarbonate, such as sodium, potassium or lithium bicarbonate, may be used as the acid acceptor instead of a carbonate. This aqueous solution is intimately mixed with dibasic acid chloride dissolved in a substantally water-immiscible organic solvent which is chemically inert to both the reactants and the reaction products and in which the resulting N,N-bis-l,2-alkylenamide is soluble. The N,N-bis-alkylenamide monomer reaction product is then recovered in a relatively pure, stable state in high yield from the organic solvent, in which it collects as the reaction proceeds, by evaporating the solvent. This process of producing the monomers has been found to be the only one which eifectively minmizcs attack on and decomposition oi the N,N' -bisalkylenamide by hydrogen chloride formed during the course of the reaction.

In order more clearly to disclose the preparation of the intermediate bis-amide compounds, specific examples of the preparation of some of them will now be described. All parts in these examples are by weight unless otherwise designated. i

A. Preparation of N,N'-bis-1,Z-ethylenisosebacamide.- A solution of about 95.6 parts of isosebacoyl dichloride prepared from isosebacio acid" (a product of the US. Industrial Chemical Company consisting of 72-80 percent of 2-ethylsuberic acid, 12-18 percent of 2,5-diethyladipic acid and 6-l0 percent of n-sebacic acid) dissolved in 400 parts of diethyl ether is added dropwise with cool ing and vigorous stirring to a flask containing a solution of parts of potassium carbonate, 800 parts of water and 43 parts ofi ethylenimine. The temperature of the mixture is maintained below 15 C. and the acid chloride is added at a rate of approximately one part per minute. The reaction mixture is allowed to warm gradually to room temperature, while stirring, for an additional hour. During the total reaction period, the pH of the reaction mixture has dropped from approximately 12.5 at the beginning of the reaction to about 8.6 at the end. The ether layer is separated, dried over solid anhydrous sodium hydroxide at 0 C. for 1 hour, the sodium hydroxide is removed by filtration and the other removed from the filtrate under reduced pressure. The resulting reaction product, N,N'-bis-l,2-ethylenisosebacamide remains as a water-White liquid. The yield is 93 percent of theoretical. When subjected to analysis the product is found to contain 10.8 percent nitrogen and 33.3 percent azirane radical as compared wtih the calculated values of 11.1 percent and 33.3 percent, respectively.

B. Preparation of N,N'-bz's-1,2 butylenisosebacamide.- To a reaction flask equipped with a stirrer, thermometer, condenser and dropping tunnel is charged a solution of about 55.2 parts of potassium carbonate and 15.8 parts of 1,2-butylenimine in 200 parts of water. The solution is stirred and cooled to about 4 C. To the cooled solution is than added dropwise, with stirring and cooling, over a period of about 23 minutes, a solution of about 23.9 parts of isosebacoyl dichloride dissolved in 72 parts of diethyl ether. During the addition, the temperature of the reaction mixture is maintained at about 4-8 C. After the addition is completed, the mixture is allowed to warm gradually to room temperature (21 C.) and stirring is continued for about 12 hours. During the course of the reaction the pH falls from pH 12.5 at the beginning to about pH 10.0 at the end. The ether layer is separated and dried by storing over anhydrous sodium hydroxide pellet-s for 1 hour at C., the pellets are removed by filtration and the ether evaporated. The resulting N,N-bis-l,Z-butylenisosebacamide remains a water white liquid. The yield is about 90 percent of theoretical. When subjected to analysis the N,N'-bis-1,2-butylenisosebacamide thus prepared was found to contain 0.6 percent chlorine and 43.1 percent Z-ethylazirane radical as compared with the calculated values of 0 percent and 45.5 percent, respectively. I

It will be obvious that the curing agents employed herein are prepared by selecting the appropriate 1,2-alkylenimine and dicarboxylic acid chloride, which are condensed by the procedures set forth above. In this way, the following compounds, which are further illustrative of the curing agents of the invention, are prepared, having the noted properties:

Compound M.P. C. Appearance N,N-bis-1,2-ethylensebacamide. 59. -61 White, crystalline solid. N,N-bis-l,2-ethylenazelamide. 44-46. 5 Do. N,N-bis-l,2-ethylendodecane- 74-76 Tan-coloredsolid.

dicarboxylic acid amide.

N,N' bis-l,2-pr0pylensebac- 31. 432. 5 White, crystalline solid.

am e.

N ,N;bis-1,2-propylenisosebac- Water-White liquid.

am e.

N,N;bis-l,2-ethylenisophthm 76-78 White, crystalline solid.

amide.

N,N'-bis-1,2-butylenisophthal- Water-white viscous liqamide. ui

N,N-bis-1,2-prcpyleniso- Water-white liquid.

phthalarnide.

N,N-bis-1,2-ethylentere- 140 White, crystalline solid.

phthalamicle.

N,N-bis-l,2-propylenterc- 96-108 D0.

phthalamidc.

N, -bis-1,2-hntylentere- 98-110 Do.

phthalarnide.

In the same Way, there are prepared the other N,N'- biS-LZ-alkylenamides described hereinabove.

II. THE EPOXY RESINS Epoxy resins in general are suitable for use in the present invention. These epoxy resins are complex polymeric reaction products of polyhydric phenols with polyfunctional halohydrins such as epichlorohydrin and glycerol dischorohydrin. Usually the difunctional chlorohydrin is used in proportion in excess of that equivalent to the polyhydric phenol and less than that which is twice the equivalent amount. The reaction is carried out in the presence of caustic alkali which is suitably employed in at least the quantity necessary to combine with the halogen liberated from the halohydrin, and usually is employed in excess. The products obtained may contain terminal epoxy groups or terminal epoxy groups together with terminal primary hydroxyl groups. In the complex reaction mixture the terminal epoxy groups are generally in excess of the terminal primary hydroxyl groups. Typical polyhydric phenols include resorcinol and the various bisphenols resulting from the condensa tion of phenol with aldehydes and ketones such as formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, and the like. The essential feature of the epoxy resins used in the compositions of the invention is the presence therein of functional epoxy groups. The remainder of the molecule, which ordinarily does not enter into the reaction with the ethyleneimine ring, may to some extent influence the properties of the polymer finally obtained.

The molecular weight of the epoxy resins can be controlled by the relative proportions of the reactants, as

well as by the extent to which the reaction is carried out. The molecular weight of the resin is not critical since both very low molecular weight resins and very high molecular weight resins can be copolymerized with the bis-amides. The properties of the cured resin compositions may of course vary with the molecular weight of the epoxy resin employed as well as the nature of the bis-amide employed. They can be made of varying melting points, epoxide contents, and degrees of polymerization from liquids and soft resins to harder resins of higher melting point. In general these resins, unless too highly polymerized, are soluble in certain organic solvents, generally in ketones such as acetone, methyl ethyl ketone, diacetone alcohol, cyclohexanone, etc., and these can be used as diluents.

An area of particularly great value of the copolyrners of the invention lies in providing resins of improved handling properties for use in applications in which high heat stability and strength are required. The particular epoxy resins heretofore used because they have these properties are high melting solids, and have been found to be extremely hard to handle, to apply (for example, they do not wet surfaces well) and to cure. It has in fact been necessary to use these resins in solution in volatile solvents in most application. The solvents of course introduce many additional problems as compared to a solvent-free, percent solids-forming resin. Thus, for example, bubbles may be trapped adjacent to material coated or encapsulated, the shrinkage caused by the volatilization of solvents during curing may cause undesirable stresses and strains, the solvent vapors may prove to be obnoxious and/ or hazardous and create additional problems of vapor recovery or disposal, additional expense is introduced into the system, etc. These difficulties have continued to be major ones in the commercial development of epoxy resins of this type. At the same time, the demand for resins having the characteristics of high heat resistance and great strength has become increasingly larger. They are used as structural adhesives for use in new high performance aircraft, in reinforced plastics used to fabricate aircraft rad-omes, ducting, structural sections, missile bodies for heated plastic dies, etc.

Certain of the copolyrners produced according to the present invention have been found to obviate all of the above-described dithculties in handling, application and curing without sacrificing the needed ultimate properties previously associated only with the difiiculty handled, high melting solid epoxy resin prepolymers. Such copolymers can be prepared by dissolving a suitable highmeiting solid epoxy resin in a liquid bis-amide, such as, for example, N,N'-bis-l,Z-ethylenisosebacamide, adding a catalyst if desired, for example, a latent catalyst of the dihydrazide type. Such resin systems have been found to have excellent handiing, application, Wetting and curing properties, and, when cured, to have ultimate properties of heat stability, strength, etc. at least equal to those of the corresponding epoxy homopolymers.

Another area for which the copolyrners of the present invention appear especially suited is that of laminating resins for rigid plastic tubing. Certain of the bis-amide copolyrners, particularly those of the aliphatic bis-amides, have excellent compatibility, processing and curing characteristics. Impact resistance of these copolyrners is often much higher than the impact resistance of comparable epoxy resins. Precise mold reproduction is possible because of the extremely low shrinkage during curing and the low temperatures required to cure them. In some cases, harder cured resins result from initially lower viscosity liquid systems, compared with comparable epoxy resins.

In order more clearly to disclose the nature of the copolymers of the present invention, a number of examples illustrating their preparation and evaluation will now be described. It should be understood, however, that this Example 1 Tlhree copolymer lots according to the present invention are prepared utilizing the following proportions of ingredients:

Lots

A B C "Epon 828 epoxy resin 100 100 100 N,N'-bis-l,2-ethylensebacamide 54 108 216 Pyromellit-io dianhydrlde 54. 4 82 136 1 A liquid coudendsation polymer of epichlorohydrin and Bisphenol A having an epoxide equivalent of 175-210, an average molecularweight of 350-400 and a viscosity at 25 0. in the range of from 5,000l5,000 centipoises and which is available commercially from the Shell Chem cal C0. of New York.

These resin mixtures are prepared by stirring the finely ground solid bis-amide and catalyst into the liquid epoxy resin at room temperature until a uniform dispersion or slurry is produced.

Three lots of 12 ply glass fiber-reinforced plastic sheets are prepared using these resin mixtures and the resulting reinforced plastics are given the same lot designations as the mixtures from which they are respectively made. The 1?. ply laminates are prepared as follows: an excess of the particular resin mixture to be used is applied to a finished glass fabric, the excess is removed and the remaining resin is smoothed and forced into the fabric by pulling it between the nip of two steel bars. The resin coated fabric is then cut and stacked in piles of 12 plies each. These piles are placed between steel platens, previously coated with a silicone-type mold release agent and heated to 155 C. The laminates are then cured between the heated platens in an hydraulic press for 20 minutes at 25 p.s.i., the temperature of the platens being maintained at 155 C. during this time. The laminates are then post-cured for 14 hours at 175 C.

in an oven. The following data is obtained from tests run on the resulting laminates:

Lots

A B C Resin contents (were as. 1 35. 9 40.9 Flex tti ral properties (A S'IM 13-790- 55.1 57.6 53. 1 2. 07 2. 46 l. 79 B B B 41. 6 49.0 39.1 1. 91 2. 26 1. 63 B B B 27. 7 29. 1 49. 6 1. 59 1. 70 1. 11 B B B 4. 6 3. 3.4 0.36 0. 26 0.15 Failure L. D D D Impact and compression strength: Impact Stre gth (Izod) (ft. lbs./

inch) (ASTM D256-5fi) 16.6 15.9 13.2 Ultimate stren th in compression (13.5;i.) (ASTM D09554) 4.17X 3. 6X10 2. 45x10 Failure 2 E B E Begin loss data after exposure at 260 liesin in Laminates before heating (percent) 38. 7 35. 9 40. 9 Resin loss at 16 hrs. (per.ent)- 16. 5 15. 7 16. 2 Resin 1155 at 60 hrs. (perrent) V 21.7 21.3 22. 7 Resin loss at 108 hrs. (percent).... 3 25. 6 28. 1 Etiects of heat aging on flexural properties: I

1 Failure of specimens: B, break; D, delarnhiation.

- Failure: B, break in body of specimen; E, edge failure.

3 These tests run at room temperature after heating laminates 228 hrs. at 260 C.

N0rE.-.SF is the fiexural strength or modulus of rupture and En is the modulus of elasticity in bending of the laminates.

Example 2 A mixture of about 12.4 grams of N,N'-bis-1,2-ethylensebacamide, 37.4 grams of epoxy resin which is a liquid condensation polymer of epichlorohydrin and bisphenol A having an epoxide equivalent of 185-200, an average molecular weight off 350-400 and a viscosity at 25 C. in the range of from 10,500 to 19,500 centipoises (and which is available commercially under the trademark ERL-2774 from the Bakelite Co., a division of the Union Carbide and Carbon Corporation), 43.7 grams of a polyalkylene polysulfide prepolymer which is a thiolterminated liquid polymer of bis(ethylene oxy)methane having a viscosity at 25 C. of 7-12 poises, a number average molecular weight of 1,000 and a pour point of 15 P. (which is available commercially under the trade designation of LP-3 from the Thiokol Corporation of Trenton, New Jersey), and 6.5 grams of triethylene tetramine is provided. The mixture is prepared as follows: first, the bis-amide is dissolved in the epoxy resin with stirring and mild heating. The trie-thylene tetramine is then dissolved at room temperature in the polyalkylene polysulfide prepolymer and the two liquid solutions are mixed together with agitation. The ingredients of the system react and cure at room temperature, and after mixing are promptly poured into a mold. Within a few hours this liquid resin system has cured tackfree. At the end of 24 hours it is found to have a hardness, measured on the Shore A-2 scale, (ASTM D676- SST) of 46. The resin is light yellow in color and exhibits good mold reproduction, flexibility and toughness.

Example 3 About 6.3 grams of N,N'-bis-1,2-ethylensebacamide are stirred into 10 grams of ERL-2774 epoxy resin pre-. viously warmed to 65 C. and agitation is continued until the bis-amide has dissolved in the epoxy resin. 4.07 grams of calcium carbonate filler are then mixed into the warm resin solution and the resulting mixture is cooled to room temperature. Finally 2 grams of melted m-phenylene diamine are added to the mixture with agitation. Agitation is stopped, the mixture is poured into a mold and is heated for 1 hour at C. The resulting rigid, tan-colored resin is designated as lot A.

A second lot of resin, designated as lot B, consisting of 10 grams of ERL-2774 epoxy resin, 6.3 grams of N .N'bis-1,2-ethylenesebacamide, 8.16 grams of calcium carbonate filler and 3 grams of m-phenylene diamine is prepared and cured by the same procedure.

The results of hardness tests run on these samples are as follows:

9 Example 4 About 5.0 grams of adipyl dihydrazide are dispersed in a solution of 6.3 grams of N,N-bis-1,2-ethylensebacamide in grams of BEL-2774 epoxy resin, placed in a mold and cured for 1 hour at 125 C. The resulting transparent, light yellow casting has a hardness (Rockwell L) of 106 and a heat distortion temperature (ASTM 13648-451) of approximately 66 C.

Example 5 A mixture of 14.05 grams of N,N'-bis-1,2-ethylensebacamide, 42.25 grams of ERL-2774 epoxy resin, 0.45 gram of resorcinol, 37.60 grams of polyalkylene polysulfide prepolymer LP-3 and 5.65 grams of tridimethyl amino methyl phenol is prepared. The bis-amide is dissolved in the epoxy resin with stirring and mild heating after which the resorcinol is added and dissolved. The tridimethyl amino methyl phenol is mixed into the poly alkylene polysulfide prepolymer and the two liquid fractions are then combined with agitation, placed in a mold and allowed to cure at room temperature. The system is tack-free in minutes. After 24 hours at room temperature a transparent, amber-colored resin having a Shore A2 hardness value of 64 has been formed.

Example 6 About 3 grams Epon 828 epoxy resin, 3 grams of N,N'-bis-l,Z-ethylenisosebacamide and 0.8 gram of diethylene triamine are mixed thoroughly at room temperature. The resulting mixture cures to a hard, tough resin in 50 minutes at room temperature.

Example 7 About 100 parts or" N,N-bis-1,2-ethylenisosebacamide and 200 parts of Epon 828 epoxy resin are mixed thoroughly at room temperature. The mixture is heated to 50 C. and 12 parts of a 75 percent solids solution of boron tiifiuoride-monoethylamine in acetone (75 parts of boron trifluoride-monoethylamine complex and 25 parts of acetone) are added with continuing agitation. The initial viscosity of the resulting mixture is 450 com tipoises at 25 C. (when measured on a Brookfield viscometer) and its pot life is in excess of 18 hours at ambient temperature. it cures in 2% hours at 121 C. to a slightly tacky, amber-colored resin.

A similar result is obtained when the procedure is repeated utilizing parts of the boron trifluoride monoethylamine-acetone solution.

Exan'zple 8 About 100 parts of a finely ground epoxy resin which is a brown solid condensation polymer of epichlorohydriu and the tetra-bis-phenol reaction product of phenol and glyoxal having a melting point of 77 C. (Durrans), an epoxide equivalent of 208 and an average molecular weight of 77 (which is commercially available under the trademark Epon 1310 from the Shell Chemical Company of New York), are stirred into 100 parts of N,N'- bis-1,Z-ethylenisosebacamide. The resulting resin solution is used to prepare a 12-ply glass fiber-reinforced laminated sheet using the procedure and glass fabric disclosed in Example 1. The laminate is cured in a hydraulic press with heated platens for 20 minutes at 155 C. and pounds per square inch pressure and then postcured for 14 hours at 175 C. The following data are obtained from tests made on this laminate.

Resin content (percent) 35.2 Flexural properties (01 laminate) At 25 C.

SF X 10* 66.1 E 10- 2.19 Failure 1 B At 150 C.

SF X 1 0* 39.6 E 1 0 1.96 Failure 1 B 10 Flexural properties (of laminate)-Continued At 204 C.--

SFX 10* 21.2 E XIO 1.64 Failure 1 B and D At 260 C.

SF x 10- 11.0 E X 10- 1.20 Failure D Resin loss data after exposure at 260 C.:

Resin in laminate before heating (percent) 35.2 Resin loss at 16 hrs. (percent) 8.49 Resin loss at 60 hrs. (percent) 12.5 Resin loss at 132 hrs. (percent) 16.0 Flexural properties (these tests run at room temperature after heating laminates 204 hrs. at 260 C.):

Resin in laminate after heating (percent) 27.63 Percent of resin lost during heating 21.5 SF 10- 20.528 E X 11% 2.27 Failure 1 D Failure of specimens: B, break; D, dela-mination.

Example 9 About 50 parts of Epon 1310 epoxy resin, 50 par-ts of N,N-bis-l,2--ethylenisosebacamide and 27 parts of 4,4- diamino diphenylsulfone are mixed thoroughly with heating and the resulting low-viscosity liquid resin system is poured into an open mold and cured by heating for 2 hours at 120 C., to a bubble-free casting of a darkcolored solid resin having a hardness (Rockwell) of M1*00. A relative test of the lowest temperature at which the resin fails to resist plastic flow under an applied load consists in measuring the temperature at which a weighted bar will deform a cured resin specimen having uniform rectangular cross section of 0.5" x 0.625". The resin specimen is placed in a temperature controlled test chamber and a /2 diameter bar bearing a load of 3 pounds is placed against the sample and the bar is /2". The bar begins to deform this resin sample at a temperature of 145 C., thus indicating excellent resistance to plastic flow at elevated temperatures. The temperature at which deformation begins in this test will sometimes be referred to herein as modified heat deformation point.

About 100 parts of finely ground Epon 1310 epoxy resin are added to 100 parts of N,N'-bis-1,2-ethylenisosebacamide with agitation and at a temperature of about C. This mixture is cooled and 54 parts of 4,4-diamino diphenylsulfone are added with agitation. When the resulting slurry has become uniform, it is poured into an aluminum mold which had been previously coated with a silicone mold release agent. This mixture is then cured for 3 /2 hours at 65 C., 1% hours at C., 13 hours at C., 24 hours at 178 C. and 1 hour at 204 C. The following data are obtained from tests run on this resin.

Physical properties:

Tensile strength (p.s.i.) (ASTM D638- 5 6T) 1 6,280 Elongation (percent) (ASTM B638- 561) 1 0.058 Modulus in tension (p.s.i.) (ASTM 13638-561) 5.0 l0 Flexural strength (p.s.i.) (ASTM D790- 49T) 13,824 Modulus in flexure (p.s.i.) (ASTM D79049T) 48x10 Compressive strength (p.s.i.) (ASTM D69554) 34,600 Modulus in compression (p.s.i.) (ASTM' I 11 Physical propertiesContinued Compressive strain at failure (percent) (ASTM 13695-54) 17.2 Compressive yield stress (p.s.i.) (ASTM D695-54) (2) Compressive yield strain (percent) (ASTM D695-54) (2) impact strength (Izod) (ft. lbs./in.) 0.32 Hardness, Rockwell E-73 Heat distortion C.) 176 Electrical properties:

Dissipation factor (1 kc.) (ASTM D150- 54T) 0.0102 Dielectric constant (1 kc.) (ASTM Aging proper-ties:

Water absorption, 24 hr. (percent) (ASTM D570) 30 C .260 Water absorption, 1 week (percent) 30 C. 0.793 Weight loss (200 hrs/500? F.) (percent) 15.2

1 .1 aw break. 5 No yield point.

Example About 100 parts of finely ground Epon 1310 epoxy tests run on this resin.

Physical properties:

Tensile strength (p.s.i.) 4,036 Elongation (percent) 0.084 Modulus in tension (p.s .i 6.72 10 Flexural strength (p.s.i.) 9,072 Modulus in fiexure (p.s.i.) 445x10 Compressive strength (p.s.i 43,100 Modulus in compression (p.s.i.).... 549x10 Compressive strain at failure (percent) 18.2 Compressive yield stress (p.s.i.) (1) Compressive yield strain (percent) (1) Impact strength (Izod) (ft. lbs./in.) 0.28 Rockwell hardness"; E-74 Heat distortion temperature C.) 195 Electrical properties:

Dissipation factor (1 kc.) 0.0624 Dielectric constant (1 kc.) 4.44

Aging properties:

Water absorption, 24 hrs. (percent) 0.370 Water absorption, 1 week (percent).. 1.07

1 No yield point.

A copolymer consisting of 100 parts of Epon 1310 epoxy resin, 100 parts of N,N'-bis-1,Z-ethylnisosebacamide and 4 parts of boron trifluoride-monoethylamine is prepared. The finely ground epoxy resin is stirred into the liquid bis-amide and agitation is continued, with moderate heating, until solution is complete, after which the boron trifluoride-monoethylamine is added and dissolved, the agitation and moderate heating being continued. The resulting liquid resin system is utilized to prepare a 12 ply glass fiber-reinforced plastic laminated sheet using the procedure and glass fabric disclosed in Example 1 hereof. The resin, however, is maintained at about 40 C. while saturating the glass fabric. The laminate is cured in a hydraulic press with heated platens for minutes at 155 C. and p.s.i. and then postcured for 4 hours at 120 C. and 14 hours at 175 C. The

following data is obtained from tests run on these laminates.

Resins content (percent) 36.7 Flexural properties (of laminates) At 25 C.:

SF X 10- 64.2 E X 10- 2.22 Failure 1 B At 150C;

SF X 10- 35.9 E X 10" 1.86 Failure 1 B At 204 C.:

SFXIO" 21.2 E X 10- 1.34 Failure 1 B At 260 C.'.

SF X 10- 13.1 E X 10- p 1.43 Failure 1 D Resin loss data after exposure at 260 C.:

Resin in laminate before heating (percent)-.. 36.7 Resin loss at 16 hrs. (percent) 5.94 Resin loss at 60 hrs. (percent) 10.7 'Resin loss at 108 hrs. (percent) 13.4 Flexural properties (of laminate) these tests run at room temperature after heating laminate 228 hrs. at 260 C.:

Resin in laminate after heating (percent) 29.98 Percent of resin lost during heating 18.3 SFXIO- 15.594 E 10- 2.29 Failure 1 D Failure of specimens: B, break; D, delzrmination.

Example 11 About 5.0 grams of adipyl dihydrazide are dispersed in a solution of 6.3 grams of N,N'-bis-1,2-ethylenisosebacamide and 10 grams of ERL-2774 epoxy resin. This solution is poured into a mold and cured for 1 hour at C. and 20 minutes at 180 C., and forms a rigid resin. The heat distortion temperature of this resin is approximately 85 C.

Example 12 About 4.86 grams of isophathalyl dihydrazide are dispersed in a solution of 6.3 grams of N,N-bis-l,2-ethylenisosebacamide in 10 grams of ERL-2774 epoxy resin. This dispersion is quite stable and can be stored for periods of up to 1 month at room temperature without appreciable change in viscosity.

A /2 inch thick piece of plate glass is coated with this resin and a second piece of glass is carefully pressed against the resin coating to avoid the entrapment of air. The resulting laminate is then cured at contact pressure for 1 hour at C. and /2 hour at C. The cured laminate is transparent and resists a tensile stress of 1,000 pounds per square inch applied in a direction perpendicular to the plane of the glass-adhesive bond.

Example 13 About 50 parts of N,N-bis-1,2-ethylenisosebacamide and 10 parts of Epon 828 epoxy resin are mixed thoroughly at room temperature and the mixture is heated to 80 C. with agitation. Forty parts of crushed Epon 1310 epoxy resin are added slowly with agitation and the mixture is cooled to 50 C. Five parts of boron trifluoride-monoethylamine are added as a 75 percent solids solution in acetone with continuing agitation. The initial viscosity of the resulting mixture is 620 centipoises at 25 C. (when measured on a Brookfield viscometer). The temperature of the mixture is maintained at 25 C. and its viscosity is measured after various time intervals as follows: After 1% hours the viscosity of the mixture is 1800 centipoises, after a total of 2 hours the viscosity agent grade).

is 2480 centiposes, after a total of 6 hours the viscosity is 4600 centipoises and after a total of 23 hours the viscosity is 40,000 centipoises. After an additional cure cycle of 2 hours at 121 C. the mixture has formed a hard, brown colored resin.

I About 50 parts of N,N'-bis-1,2-ethylenisosebacamide and 30 parts of Epon 828 epoxy resin are mixed thoroughly at room temperature and the mixture is heated to 80 C. with agitation. Twenty parts of crushed Epon 1310 epoxy resin are added and the mixture is cooled at 50 C. Five parts of boron tritiuoride-monoethylamide (in a 75 percent solids solution in acetone) are added with continuing agitation. The initial viscosity of the resulting mixture is 700 centipoises at 25 C. (when measured on a Brookfield viscometer). It cures in 3 hours at 121 C. to a hard, brown colored resin.

The previous preparation is repeated except that 25 parts of powdered calcium carbonate filler are added. The initial viscosity of this mixture is found to be 1000 centipoises and it also cures to a hard, medium-brown colored resin.

About 50 parts of N,N'-bis-1,2Tethylenisosebacarnide and 40 parts of Epon 828 epoxy resinare mixed thorr oughly at room temperature and the mixture is heated to 80 C. with agitation. Ten parts of crushed fEpcin 1310" epoxy resin are added and the mixture is cooledto. 50C. Five parts of boron trifiuoride monoetliylaminefin a 75 percent solids solution in acetone) are added with continuing agitation. The initial viscosity of the resulting mixture is 260 centipoises at 25 C. (when measured on a Brookfield viscometer). It cures in 3 /2 hours at 120 C. to a hard, light brown resin.

. The previous preparation is repeated except that 25 parts of powdered calcium carbonate filler are also added. The initial viscosity of the resulting mixture is 500 centipoises and it also cures to a hard, light brown resin.

Example 14 About 50 parts of N,N'-bis-1,2-ethy1enisosebacamide and 10 parts Epon 828 epoxy resin are mixed thoroughly at room temperature and the mixture is heated to 80 C. with agitation. Forty parts of crushed Epon 1310 epoxy resin are added andthe mixture is then cooled to 50 C. Three parts of boron trifluoride-monoethylamine and 10 parts of pyromellitic dianhydride are added in finely divided form with continuing agitation. The resulting mixture is quite reactive and has a pot life of approximately 1 minute after-mixing. It cures to a hard, dark brown resin. For use, the mixture of resins is placed in the mold and'the curing agents are added thereto with stirring. An exotherm is noted during curing.

Example 15 Monomeric polychlorophenyl-bis (4- glycidoxy-phenyl) methane is prepared as follows:

' A. In a vessel provided with external heating means, addition device, thermometer, mechanical agitator and efficient reflux condenser attached to a gas absorption system are placed 6110 parts (45.3 moles) of technical sulfuryl chloride, 62 parts of sulfur monochloride and 19 parts of anhydrous aluminum chloride (analytical re- The addition device is charged with 800 parts (4.87 moles) of benzal chloride and addition thereof is commenced with vigorous agitation of the contents of the vessel and circulation of ice-cold water in the condenser.- Moderate heating is applied so that the temperature in the vessel reaches about 41 C. and further rises to about 43 C. during the beginning of the addition. Addition is at a rate such that about 200 minutes are required in all and the temperature is then at about 35 C. The copious volumes of gas evolved, comprising S HCl and some C1 are absorbed in the gas absorption system. At the end of the addition the reaction mixture is heated first to 55 C. in about 100 i i minutes and then gradually to 60 C. during about 7.5 hours further. The mixture is then distilled at reduced pressure, first at about 650 mm. Hg and then at about 25 mm. Hg pressure until the contents of the vessel reaches 70 C. and most of the unreacted sulfuryl chloride has been removed.

The reaction mixture is then quenched in 8000 parts of boiling water employing steam to efiect agitation during the quenching. The strongly acidic aqueous layer is decanted and the heavy oily organic layer is washed first by repeated steaming with a further 8000 parts of boiling water and then is washed successively with about 1000 parts of about 5 percent aqueous sodium bicarbonate solution and about 1000 parts or water at about 50 C. About 350 parts of chloroform are added to the oily layer after separation from the last aqueous wash and the resulting chloroform solution is dried by agitation successively with 25 parts each of anhydrous mage nesium sulfate and anhydrous potassium carbonate. The dried chloroform solution is separated and distilled at temperatures increasing upto 100 C. at 5 mm. Hgpressure to remove the chloroform. The residual 1470 parts of yellowish oil has n ,=1.6157 and largely crystallizes on standing at room temperature. The melting, point ofthe mixture is not'sharp as it consists of a mixture of tri-,' tetraand penta-chlorobenzal chlorides together withvarious by-products of the reaction such as benzene hexachloride.

Analysis.Calculated for C H Cl Cl, 71.2 percent. "Found: CI, 70.4 percent.

The empirical formula is calculated to average about 7 2.3 5.7-

B. Preparation of polychl0r0benzaldehyde.A vessel arranged for external heating and fitted with thermometer, mechanical agitator and exhaust line to a gas absorption system is charged with 9000 parts of 96 percent sulfuric acid (reagent grade) and 1470 parts of the polychlorobenzal dichloride of Example A and is then heated rapidly with agitation to about C. The vigorous evolution of hydrogen chloride is controlled by reducing the rate of stirring. More heat is applied as needed to maintain the temperature at about 80 to C. for 1 hour and then to raise the temperature to about to C. where it is maintained for a further five hours. The reaction mixture is then cooled slowly with gentle agitation to permit the formation of a granular precipitate comprising the unhydrolyzable contaminants such as benzene hexachloride which are then collected. The clear filtered solution is poured into a large excess of cracked ice and the precipitated polychlorobenzaldehyde 1s collected, washed repeatedly with several volumes of warm water, with about 5 percent aqueous sodium carbonate solution, and again with Warm water and col lected. The polychlorobenzaldehyde is dried in a circulating oven at 40 to 45 C. to furnish 926 parts of light tan powder having a melting point range of 100 to 105 C. A further yield can be obtained by repeating the process with the unhydrolyzable material consisting mainly of benzene hexachloride recovered above, which also contains an amount of unhydroiyzed polychlorobenzal chloride, the polychlorobenzaldehyde thus pre pared is found to be a mixture of tri, tetraand pentachlorobenzaldehydes.

Analysis.Calculated for C Found: Cl, 58.4 percent. qHzCLiO. CI 58.2 percent.

C. Preparation of polyhaloaryl bisphenol.ln a vessel provided with external steam heating and fitted with thermometer, mechanical agitation and an exhaust port are placed 1740 parts (18.5 moles) of phenol, parts of Water, 800 parts of 96 percent sulfuric acid and about 3 parts of .thioglycollic acid. To this mixture are added in portions 650 parts (2.2 moles calculated as tetra-chlorobenzaldehyde) of the polychlorobenzaldehyde of Example B. (ground to. a 20 mesh size) over a period of 1 hour while maintaining the temperature atabout 40 C. by external cooling when needed. After stirring for another hour, the reaction mixture is heated to about 65 to 70 C. and maintained there for about'a further hour. At this time a test sample of the thick syrupy reaction mixture is found to be completely soluble in an excess of dilute sodium hydroxide and the reaction mixture is diluted with 200 parts of water and steam-distilled to remove unreacted phenol. The tacky brown lumps which form are separated from the acidic aqueous layer and dissolved by boiling with four successive 3000 part portions of about 1 to 2 percent aqueous sodium hydroxide. A small amount of tarry residue remains on the walls of the vessel and is discarded. The four alkaline solu tions are combined and neutralized to a pH of about 85 by addition of an excess of powdered solid carbon dioxide with vigorous stirring. The product, which consists of a mixture of the tri-, tetra; and pentajchlorophenyl bis-.(4-hydroxyphenyl) methanes thusprepared, is pre; cipitated in a readily fiJt erable form and is collected, washed with cold water and dried at about 65 C. It has a melting point of about 185 to 190 C. and on analysis is found to contain 31 .1 percentof chlorine.

D. Preparation of a glycidyl polyether of polychloro phenyl bisphenbL-In a vessel provided with external heating and fitted with addition funnel, stirrer, thermometer and reflux condenser are placed 900 parts (3.82 equivalents by titration) of the polychlorophenyl-bisphenol of Example C and 2090 parts (22.6 moles) of commercial epichlorohydrin and this mixture is heated to refluxing (about 95 C.). A solution of 163 parts (4.07 moles) of sodium hydroxide in 820 parts of anhydrous methanol is added to the vessel during about 2 hours and heating and stirring is continued for 2 hours longer. After cooling to room temperature, the reaction mixture is filtered to remove the precipitate of sodium chloride which forms and the filtrate is distilled at temperatures increasing to 120 C., at 0.5 mm. Hg pressure, to remove methanol and unreacted epichlorohydrin. The clear brown residual resin is readily pulverized on cooling and is substantially tack-free, i.e. the powder does not clump. This prepolymer consists essentially of polychlorophenylbis(4-glycidoxy-phenyl)-methane and is a mixture of the tri-, tetraand penta-chloro compounds. It contains 5.3 percent oxirane oxygen and 29.1 percent chlorine and has the molecular weight 621, as determined ebul lioscopically in benzene. It softens to a'flowable material at about 95 C.; Durrans mercury method melting point is about 75 C.

About 100 parts of polychlorophenyl-bis(4-glycidoxyphenyl)-methane and 100 parts of N,N-bis-1,2-ethyl enisosebacamide are blended together while being warmed sufficiently to form a solution and 2 parts of boron trifiuoride monoethylamine are subsequently added. The resulting mixture is poured into an open mold and cured for /2 hour at 150 C. and 17 hours at 177 C. to form a hard, resilient, tough, transparent, and red: dish-brown casting. Its fiexural modulus at room tem perature is 4.0 10 and its hardness on the Rockwell L scale is 111.

A 12 ply glass fiber-reinforced plastic laminate is pre; pared from this resin composition using the procedure and glass fabric disclosed in Example 1. The laminate is then cured in a hydraulic press for 2 hours at 300 F. and 400 pounds per square inch pressure and then post cured for 19 hours at 250 F. The following data is ob: tained from tests run on this laminate.

Flexural properties:

SF 3 88 E XlO 4.2 100." (3.:

st= 10 E 10 6.9

Tensile strength at 25 -C. (p.s.i.) 20,000 Resin loss after exposure for 2 hrs. at 260 C.

(percent) 1.54

Example 1 16.

About parts of triglycidylcyanurate (a white, crystalline product which melts between 30 and 50 C. and which is prepared by therriethod disclosed in US. Patent 2,741,607, are melted and mixed thoroughly with 100 parts of liquid N,N-bis-1,2-ethylenisosebacamide. Four parts of finely ground boron trifluoride monoethylamine are then added with agitation. The resulting mixture, a low viscosity liquid at room temperature, is cured for 64 hour t F The tess tine'ha r i r s has a hardness (Rockwell) of M5110 The modified: heat de-,. formation point of this resin- (run according to the test explained in Example 9 hereof) is above 220 C Example 17 About 103 parts of N,N--bis -1,2-propylenisosebacamide are mixed thoroughly with 100 parts of EPOI1828 epoxy resin and 27 parts of metaphenylene diamine are then added-with agitation. The resulting mixture, which has a pot life at ambient temperatures of approximately 3 hours, cures in 4 hours or less at 121 C. to a hard, brownish-black resin.

Example. 18-

About 100 parts of N,N'-bis-l,2-propylenisosebacamide and 100 parts of Epon 828 epoxy resin are mixed thoroughly and 12 parts of menthane diamine are added with continuing agitation. The resulting mixture is found to have a pot life offrom 4 to 5 hours at ambient temperatures. When coated on a metal panel this material cures in 20 minutes at 250 F. to a clear colorless to slightly yellow tack-free resin.

Example 20 Three copolymer lots according to the present invention are prepared utilizing the following proportions of ingredients:

L t .1 l B l 0.

Epon 828 100 100 100 N,-bis-1,2-ethylenisophthala 1 108 108 108 Isophthalyl dihydrazide 24. 2 48. 5 72. 8 Dicvandiamidp 2.3 4. 2 4. 2 Primary hydrogena'ing ratio 1/3 2/3 1/1 Azirane'oxirane ratio 2 2/1 2/1 2/1 The calculated ratio of equivalents of primary amine hydrogen of the isophthalyldihydrazlde to the total number of equivalents of oxirane and aziridine rings.

3The calculated ratio of aziridine ring to oxirane ring. The- Epon 828 epoxy resin, the isophthalyl dihydrazide and the dicyandiamide constitute'nts of these lots are first milled together on a paint mill and the N,N'-

17 bis-1,2-ethylenisophthalamide is then mixed with the other constituents at about 80 C. with rapid agitation.

Three lots of 12 ply glass fiber-reinforced plastic laminates are prepared using these resins and the resulting reinforced plastics are given the same lot designations as the resins from which they are respectively made. The laminates are prepared by the process and using the glass fabric described in Example 1 hereof. No postcure is given to these lots except as indicated in the tables below. The following data is obtained from tests run on these laminates:

Lots

Resin contents (percent) 36.1 40. 9 38. Flexural properties of laminates:

Post. cured 1 hr. at 177 0.:

S XIO- 69.1 74. 5 76. 8 EnXlO 3.67 4.42 3. 93 At 150 0.:

SF 10 63. 0 70. 3 57. 6 EeXlO- 3. 28 4. 10 3.11 At 230 0.:

SFXlO- 12. 3 20. 0 6.1 EBXIO 1. 80 2. 54 1.15 Post cured 13 hr. at 177 0.:

SFXlO- 21.5 17.6 10.0 13BX10 2.04 2. 21 1. 31 Density (g lee) 1. 84 1. 72 1. 77 Heat distortion temperature C 272 275 270 Heat penetration temperature C.) l 274 259 240 Impact strength Izod (it. lbs.linch) 18. 34 14.87 14.11 Resin loss data after exposure at 260 0.:

Resin loss at 16 hrs. (percent). 14.65 15.10 18. 28 Resin loss at 50 hrs. (percent) 19.13 19. 49 21. 10 Effects of heat aging on flexural properties of laminates (tests run at rm. temperature after being heated as follows:)

No heat cycle:

SFXIO- 70.8 92. 2 70. 9 BX10 3.11 4. 59 3. 28 16 hours at 260 0.:

S XIO 14. 2 24. 6 51. 6 4. 25 4. 56 3. 60

l The heat penetration temperature is determined as follows: The resin sample is immersed in a silicone oil bath. A one kilogram load is applied to the sample through a. 1 sq. millimeter bearing surface. The oil is heated at the rate of 2 0. per minute and the temperature at which bearing surface begins to penetrate the sample is reported.

Example 21 A bis-amidezepoxy-resin copolymer prepared according to the present invention is compared (at two levels of cure) with a conventional epoxy resin formulation to indicate some of the improved properties of the former. The compositions are prepared by stirring the constituents together at about 80 C. until they are thoroughly mixed (approximately 5 minutes).

In another preparation, about 100 parts of Epon 828 epoxy resin, 216 parts of N,N-bis-ethylenisophthalamide 18 and 6.3 parts of boron trifluoride monoethylamine are combined by the same method and a 12 ply glass fiberreinforced plastic laminate is prepared according to the procedure of Example 1 hereof utilizing this resin. The laminate is then cured in a hydraulic press with heated platens for 20 minutes at 155 C. at 25 pounds per square inch and then postcured for 14 hours at 175 C. The following data is obtained from tests run on this laminate.

Resin contents (percent) 27 Flexural properties (of laminates) At 25 C.:

SF 10- 72.9 E X- 2.80 Failure 1 B At 150 C.:

SF 10- 59.4 E 10 2.84 Failure 1 B At 204 C.:

SF 1O- 34.3 E 10- 1.86 Failure 1 B At 260 C.:

SF 10- 12.7 E 10- 1.43 Failure 1 B, D

Resin loss data after exposure at 260 0.:

Resin loss at 16 hrs. (percent) 8.00 Resin loss at hrs. (percent) 15.9 Resin loss at 108 hrs. (percent) 21.8

Effects on heat aging on fiexural properties (of laminate) (these tests run at room temperature after heating laminate 200 hrs. at 260 C.):

Failure of specimens: B, break; D, delamination.

Example 22 About 100 parts of solid N,N-bis-1,2-ethylenisophthalamide are dissolved in 100 parts of Epon 828" liquid epoxy resin at a slightly elevated temperature and 24.25 parts of isophthalyl dihydrazide (previously ground to a fine powder) are dispersed in the liquid resin mixture. A finished glass fabric is then knife-coated with this resin at approximately 150 F. and the coated fabric is formed into a 16 ply laminate by heating 16 layers of coated fabric for 2 minutes at 310 F. uner contact presure and then in a heated hydraulic press for 20 minutes at 310 F. at 25 p.s.i. and finally post-curing for 40 hours at 250 F. The following data are obtained from tests 60 run on this laminate.

Resin content, percent 32 Flexural properties (of laminate):

At 25 0.: s1= 10 97.5 E XIO- 5.7 At 150 0.:

SF 10 41.4 E 10 3.0

At 230 C.:

SF 10- 14.9 E 10- 2.3 Heat distortion temperature, C 260 Heat penetration temperature, -C 260 '-:'I'h1:e.e.c polymer-lots accordingto the present :inven- .tion' areprepared utilizingthe followingproportionsz 'I hese resin mixtures are prepared by stirring the finely ground solid bis-amide into the liquid epoxy resin at 80 "(3.; continuing agitation until the bisamide has dissolved,

cooling the resulting solution to room temperature, adding the finely divided isophthalyl dihydrazideand stirring to term a uniform slurry.

" "Three lots of 12 ply glass fiber-reinforced plastic laminates are prepared from the above resin systems and the resulting reinforced plastics are given the same lot designations as the resin systems from whichtheyare respectively made. The laminates are prepared by. the procedure losed' in Example Thereof and'aresuited for 30 minthen for 13 hours at 350 F. in a circulating air oven. The following data are obtained from tests run pntheselamiiii-9 Lots A i B G Resin eontents(percent).. 48.8 43.7 I 43.0 Density (g.lce.) 1 7;! 1.65 1.63 Flex'ural properties oflamlnates 30.3 g-QZ 1 Esxm: 1. Heat dlstgrt'ionte'rnp. (f C.).. Z- 270 Heat periatrationtempJ 270 G. mpas st e gt zq l s/ c Resin lossdata'after exposure at 2609 "Resin-lesser. l6 hrs-(percent).-.

Resin loss at 50 hrs, (percent)... Efleets'of heat aging on ilexural propert esoi' =larnina'tes (tests run'at room team; after 1 being heatedas follows): .1 lgetore heating:

' -'SF l0-!; 74.0 84. 5 93.6 EBXIO-L 6.2;! f 5.32 4,75 16 hrs. at 260 FXHH 19.5 p 694 27.0 E X10:.. 6.30 r 5. 48 5.57 60hrs.at 260 C. F I 22.6 58.8

li ites at 310 F. and psi. in an hydraulic press, and

2 0 'on're is-31 0 :for '20 minutes under 25 p.-s.i. vfollowed by an oven postcure of 5 hours at.350 F. Noblistcring observed during a hot soldering test of this laminate at 230 C. thus indicating the utility .of this system for .use as a substrate for printed circuits.

:In a second preparation of a copper clad laminate, copper foil .is'bonded to a thick sheet of phenolic resin with a mixture of 216-parts by weight of N,N -bis- 1,2-ethylenisoph-thalainide, 100 parts by weight of Epon ;828'.epoxy-.-resin and 80.6 parts by weight of isophthalyl dihydrazide. This laminate is cured for 20 minutes at 310-F. and 1'000p.s.i. No blistering is observed during a hot solder test of this laminate at 230 0., thus indicating the utility of this resin as an adhesive in copper clad phenolic laminates used in printed circuits.

Example 23 A eopolyrner composition according to the present invention consisting of 109 parts of Epon 13.10 epoxy resin and 100 parts of N,N'-bis-l,Z-ethyleniSophthalamide i p p re sl y add n thes un p xy resin to the liquid bis-amide at approximately 80 C. with agitation and continuing the agitatipn until, the mixture is homogeneous.

A 1 2 ply glass fiber-reinforced plastic laminate is prepared by the procedure disclosed in- Example 1 hereof utilizing this resin. The laminate is press cured for 20 lrninutes' at 155,- C. and 25-p.s.i. and then postcured for 14 hours at 175 C. The following data are obtained irom tests run. on this laminate.

Resin content (percent) -2 23.7 Flexural properties (of laminates):

At 25 C.:

-e-'---.--- 13 X10? 2:83 Fa u ea-.- ---r-,--- B At 15.0-C.:

SFX 10- 2 61.8 E XIO- 2.47 Failure B At204 C.:

.s xw

13 x10 2.20 Eailure l B At 260 (3.:

SEX 10 10.9 EI'BXIOITG --'7"--T'.-.---T---.-----.- Failure ..L v D, B Resinloss data after exposure at 260 C.:

Resin loss at l6'hrs. (percent) 9.83 Resin loss at hrs; (percent) 14.3 Resin loss at 108'hrs. (percent) 17.1 Flexural properties (of laminate) (these tests run at temp. after heating laminate 228 hrs. at 260*(1:

E ie 2! laminat fte hea (r ma k.- 1 1$ Percent ofresin lost during heating c g 24.9 SFXIO- (p.s.i 29.975 E X lQ- (psi. 2.54 1 If??? D #Failnre; otj." specimens: B, break; D, delamination.

Emmp -2 About 100 parts of Epon 1310 epoxy resin and 60 parts of 4,4 '-diam ino diphenylsulfoneare pulverized and mixed as powders and thismixture isaddedto 100 parts of N,N'-bis -1,Zaethylenisophthalamide by the procedure of the preceding. example. The. resulting fluid mixture is e u ed. 1. 1 meld an ured e ho r a hour at .C..,. 1-ho.ur 211.120, C... l8v hours.a.t.l7& C.

n -11491.net The tello ns; ata ree tain 311 Qath re lt n a s Dielectric constant (1 kc.) Aging properties:

Water absorption, 24 hrs. (percent), 30 C. 0.498

Water absorption, 1 wk. (percent), 30 C. 1.63

Weight loss (200 hrs/500 F.) (percent) 16.0

In another preparation about 50 parts of Epon 1310 epoxy resin, 50 parts of N,N'-bis-,2-ethylenisophthalamide and 30 parts of 4,4'-diaminodiphenyl sulfone are mixed thoroughly with heating at about 90 C., placed in a mold and cured at 120 C. for 14 hours to a casting of solid resin which has a hardness (Rockwell) of M-90.

Example 25 About 100 parts of Epon 1310 epoxy resin and 2 parts of boron trifiuoride-monoethylamine are pulverized and mixed as powders and this mixture is added to 100 parts of N,N'-bis-1,Z-ethylenisophthalamide by the procedure of the preceding example. The resulting mixture is placed in a mold and cured, first in an oven at about mm. Hg pressure for 1% hours at 75 C. and /2 hour at 95 C. and then at atmospheric pressure for 2 hours at 85 C., 16 hours at 120 C., 1 hour at 150 C., 42 hours at 178 C. and 1 hour at 204 C. The following test data are obtained from tests run on this resin.

Physical properties:

Agin, properties:

Water absorption, 24 hrs. (percent) 30 C-, 0.375 Water absorption, 1 week (percent), 30 C... 1.27

1 Jaw break. 2 No yield point.

Two copolymer lots of the present invention are prepared by the same procedure utilizing the following proportions of ingredients:

Lots

Epon X-1310 epoxy resin 75 100 N,Nbis-1,2-ethylenisophthalamide 100 Boron trifluoride monoethylamine 2 4 Two lots of 12 ply glass fiber-reinforced plastic laminates are prepared using these resin systems and the resulting reinforced plastics are given the same lot designations as the resins from which they are respectively made. The laminates are prepared according to the procedure disclosed in Example 1 hereof and are cured in a heated hydraulic press for 20 minutes at 155 C. at 25 p.s.i.

22 and then postcured for 14 hours at 175 C. The follow ing test data are obtained from tests run on these laminates:

Lots

Resin content (percent) 24.7 33.8 Flexural properties (of laminates):

21. 6 19. 5 2. 54 1. 23 D B,D

. 10.12 8.32 16.1 12. 9 19.6 Resm loss at 132 hrs (per cent). 17.0 Flexural Properties (of laminate) (tests run at room temp. after heating laminates for the indicated time at 260 0.), hours 228 204 Resin in laminate after heating (percent) 17.58 27.14 Percent of resin lost during heating 28. 8 19.7 SFXlO- (p.s.i.) 26. 565 EBXIO- (p.s.i.) 1.78 Failure D 1 Failure of specimens: B, break; D, delamination.

About 50 parts of N,N-bis-1,2-ethylenisophthalamide, 50 parts of Epon 1310 epoxy resin and 2 parts of boron trifluoride monoethylamine are mixed together at room temperature and gradually heated to 170 F. until a uniform solution is obtained. The mixture is then cooled to 140 F. and hot melt coated onto vinylsilane-treated roving glass fibers having 200 ends per inch. The resin content of the coated glass fabric is approximately 35 percent. The coating qualities of this material are excellent. The Web is somewhat tacky at room temperature immediately after coating, and after aging for two weeks at room temperature the web is still flexible, thus indicating good shelf life.

A 14 ply cross-laminated panel is prepared from this saturated fabric. The panel is cured in a heated hydraulic press for 30 minutes at 325 F. and 25 p.s.i. and then oven postcured for 16 hours at 400 F. The following test data are obtained from tests run on the panel.

Resin content (percent) 31 Flexural properties of laminate:

At 25 C.:

SF 10 88.7 E XIO- 3.05 At 205 C.: SF 10- 54.9 At 260 C.: SF 10 14.9 Barcol hardness 77 Effects of heat aging on flexural properties (at 21 C. after 2 hr. in boiling water):

SF 10 60.7 E 10- 2.79 Water absorption:

Weight increase after 24 hr. immersion at rm.

temp. (percent) 1 0.57 Thickness increase after 24 hr. immersion at rm.

temp. (percent) 1 0.04

1 Tests run according to Fed. Spec. LP-406. l

Example 26 About 5 parts of N,N'-bis-1,2-ethylenisophthalamide, 5 parts of ERL-2774 epoxy resin and 2 parts of metaphenylene diamine are mixed at approximately C. with agitation until a homogeneous liquid mixture is obtained. This mixture is used to adhere chromate-etched aluminum test pieces together in overlapped relationship.

The 'test'pieces-are one inch inwidth. The liquid resin is applied to thetest pieces with a spatula and the test pieces are brought together until they touch the opposite sides of two narrow mil thick glass shims (which are usedto insure that all of the resin is not later forced from between the-test pieces). The test pieces are adhered together with an overlap of approximately 0.5 inch which is entirely filled with adhesive. The resulting test samples are placed in a hydraulic press of which the platens are held at 350 F. for 1 hour. The shear strengths at various temperatures of. the resulting bonds are tested by pulling the ends of the pairs of adheredtest pieces in tension until the bonds fail. The test is run on an Instron tensile machine with temperature controlled cabinets mounted thereon at a jaw separation rateof 0.2 inch/ minute. The following test data are obtained.

Temp. ,F.: Shear strength (psi) 67 4,070 +300 4,820

Comparison of the data the foregoing table with that obtained using a comparable epoxy resin adhesive indicates that the-use of the bis-amide comonomer in the adhesive produces not only improved high temperature strength, but also better low temperature properties.

Example 27 Example 28 7 About 99 parts of t riglycidyl cyanurate, 108 parts of N',N"'-bis-1,2 ethylenisophthalamide and 2 parts of boron trifiuoride-monoethylamine are mixed as finely divided solids at room temperature and this mixture is heated until it becomes liquid. The liquid-mixture does not immediately solidify when allowed to cool, but will remain liquid atroom temperature for more than 24 hours; This mixture is cured 40 hours at 140 F., 4 hours at 250 F. and 4 hours at 350 F. to form a hard resin having a tensile strength of 3700 p.s.i; and a modified heat deformation point (run according to the test explained in Example 9 hereof). of 235 C.. Thissample loses 305 percent of itsweightwhenheatedfor 1.65 hoursat 500 F.

Example 29 About 5.0 grams of N,N'-bis-1,2-propylenisophthalanride and 5.0 grams of Epon 828 epoxy resin are mixed at room temperature, both being liquids. About 0.05 gram of solid finely divided boron trifiuoride monoethylamine are dispersed in the resulting liquid mixture which is placed in a mold and cured for 3 hours at 150 C. The resulting hard, clear castingis light amber in color.

24 Example 30 About 100 parts of polychlorophenyl-bis (4-glycidoxyphenyl-)-methane, 100 parts of N,N-bis-1,Z-ethylenisosebacamide, 100 parts of N,N'-bis-1,2-ethy1enisophthalamide and 3 parts of boron trifiuoride monoethylamine are mixed at approximately C. until a homogeneous liquid is obtained. The resulting liquid is poured into an open mold and cured for 96 hours at 60 C. and 5 hours at 121 C. to form a hard, resilient, tough, transparent, reddish-brown casting having a hardness (Rockwell L) of 101.

The terms and expressions which have been employed are used as terms of description and not of limitation, and it is not intended, in the use of such terms and expressions, to exclude any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed.

What is claimed is: I

1. The product produced by the process of intimately contacting (1) a reaction product of a polyhydric phenol and a polyfunctional halohydrin', which reaction product contains more than one vicinal epoxy group, and (2) a polyalkylenamide represented by the formula:

0 oats-trig I EH1 orrru wherein R represents a: member of the group consisting ofadivalent aliphatic hydrocarbon radical having from 6 to 18 carbon atoms, the 1,3-phenylene radical and the 1,4-phenylene radical, and R and R each represent a member of the group consisting of hydrogen and-a lower alkyl radical.

2. The product of claim 1- in which the polyfunctional halohydrin is epichlorohydrin.

3. The product of claim 1 in which said polyhydric phenol: is: bis(4-hydroxyphenyl) dimethylmethane.

4. The product of claim 1 in which the polyalkylenamide is N,N-bis-l,2-ethylene sebacamide.

5. The product of claim 1 in which the polyalltylenamide is N,N-bis-1,2-ethylene isosebacamide.

6. The product of claim 1 in which the polyalkylenamide is N,N'-bis-1,2-ethy1ene isophthalamide.

7. The product of claim 1 in which the polyalkylenamide is N,N'-bis-1,2-propylene isosebacamide.

8. The product of claim 1 in which the polyalkylenamide is N,N-bis-1,2-propylene isophthalamide.

References Cited in the file of this patent- UNTTED STATES PATENTS 2,296,225 Ulrich Sept. 15, 1942 2,901,443 Starch et a1 Aug. 25, 1959 2,918,439 Philips et a1. Dec. 22, 1959 2,950,197 Allen et al. Aug. 23, 1960 FOREIGN PATENTS 466,270 Great Britain May 24,. 1937- 899,955 France Sept. 11, 1944 900,137 Germany Dec. 21, 1953 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No" 3,079,367 February 2-6-,--l963 Paul Fram et al.,

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 63, for "monomethylamine" read monoethylamine column 13, line 11, for "at" read to same line for "-monoethylamide read monoethylamine column 16, Example 2O in the table, first column, line 2 thereof, for "N, bisl,2" read N,N' bisl,2 column 17, Example 21, sub-column heading, for "C", first occurrence, read A column 19, first table, column 2 line 2 thereof.

for "126" read 216' Signed and s ealed this 31st day of December 1963.,

(SEAL) Attest: EDWIN L. REYNOLDS ERNEST W. SWIDER Attesting Officer Ac ting Commissioner of Patents 

1. THE PRODUCT PRODUCED BY THE PROCESS OF INTIMATELY CONTACTING (1) A REACTION PRODUCT OF A POLYHYDRIC PHENOL ANND A POLYFUNCTIONAL HALOHYDRIN, WHICH REACTION PRODUCT CONTAINS MORE THAN ONE VICINAL EPOXY GROUP, AND (2) A POLYALKYLENAMIDE REPRESENTED BY THE FORMULA: 